EP0644216B1 - Naphthalene-ring resin, resin composition, and cured product thereof - Google Patents

Naphthalene-ring resin, resin composition, and cured product thereof Download PDF

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Publication number
EP0644216B1
EP0644216B1 EP94910046A EP94910046A EP0644216B1 EP 0644216 B1 EP0644216 B1 EP 0644216B1 EP 94910046 A EP94910046 A EP 94910046A EP 94910046 A EP94910046 A EP 94910046A EP 0644216 B1 EP0644216 B1 EP 0644216B1
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EP
European Patent Office
Prior art keywords
resin
epoxy resin
formula
resin composition
represented
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94910046A
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German (de)
English (en)
French (fr)
Other versions
EP0644216A1 (en
EP0644216A4 (enrdf_load_stackoverflow
Inventor
Hiroaki Ohno
Hiromi Morita
Shigeru Moteki
Yasumasa Akatsuka
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Nippon Kayaku Co Ltd
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Nippon Kayaku Co Ltd
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Publication date
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Publication of EP0644216A1 publication Critical patent/EP0644216A1/en
Publication of EP0644216A4 publication Critical patent/EP0644216A4/xx
Application granted granted Critical
Publication of EP0644216B1 publication Critical patent/EP0644216B1/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
    • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
    • C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3218—Carbocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • This invention relates to resins with high refractive indices which are useful as sealing and laminating materials for electronic components; resin compositions containing said resins to afford cured products with high heat resistance, low water absorption and good adhesion; as well as the cured products of said resin compositions.
  • This invention provides resins which afford cured products with high heat resistance, low water absorption and good adhesion enough to endure such rigorous working conditions; resin compositions containing said resins; and the cured products thereof.
  • this invention relates to:
  • n is 0 to 10, preferably 0 to 8, more preferably 0 to 4. If n (mean value) exceeds 10, the viscosity increases to deteriorate the workability.
  • the halogen atom includes a chlorine atom, bromine atom, etc.
  • the lower alkyl group includes methyl, ethyl, t-butyl, etc.
  • the lower alkoxy group includes methoxy, ethoxy, etc.
  • the resin of formula (II) according to this invention is obtained by condensing a naphthol with a biphenyl derivative represented by formula (IV): wherein R represents a halogen atom, hydroxyl group or lower alkoxy group, if necessary, in the presence of an acid catalyst.
  • R represents a halogen atom, hydroxyl group or lower alkoxy group, if necessary, in the presence of an acid catalyst.
  • the naphthol includes 1-naphthol, 2-naphthol, 1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 4-methyl-1-naphthol, 2-methyl-1-naphthol, 8-methyl-2-naphthol, 5-methyl-2-naphthol, 4-ethyl-1-naphthol, 5-ethyl-1-naphthol, 8-ethyl-2-naphthol, 5-ethyl-2-naphthol, 5-butyl-1-naphthol, 4-chloro-1-naphthol, 5-chloro-1-naphthol, 6-chloro-1-naphthol, 4-bromo-1-naphthol, 6-bromo-1-naphthol, 4-chloro-2-naphthol, 5-bromo
  • R preferably represents a chlorine atom, bromine atom, iodine atom, hydroxyl group or a lower alkoxy group containing 4 or less carbon atoms. With alkoxy groups containing 5 or more carbon atoms, the reaction is slow.
  • Preferred examples of the biphenyl derivative of formula (IV) include 4,4'-bis(chloromethyl)biphenyl, 4,4'-bis(bromomethyl)biphenyl, 4,3'-bis(chloromethyl)biphenyl, 3,3'-bis(chloromethyl)biphenyl, 4,4'-bis(hydroxymethyl) biphenyl, 4,4'-bis(methoxymethyl)biphenyl, 3,3'-bis(hydroxymethyl)biphenyl, 3,3'-bis(methoxymethyl)biphenyl, 4,4'-bis(ethoxymethyl)biphenyl, etc.
  • the acid catalyst which can be used in the above condensation reaction includes inorganic or organic acids, for example, mineral acids such as hydrochloric acid, sulfuric acid, phosphoric acid; organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; as well as Friedel-Crafts catalysts such as zinc chloride, aluminium chloride, cupric chloride, ferric chloride; sulfuric acid esters such as dimethyl sulfate, diethyl sulfate; trifluoromethanesulfonic acid; boron trifluoride; oxalic acid; and they may be used alone or in combination.
  • the acid catalyst is preferably used in an amount of 0.1 to 30% by weight of the compound of formula (IV).
  • the naphthol is usually used 0.5 to 20.0 times, preferably 2 to 10 times in molar excess of the compound of formula (IV).
  • the reaction may be carried out in the absence or presence of a solvent such as benzene, toluene, methyl isobutyl ketone, etc.
  • the reaction temperature is preferably 40 to 180°C, and the reaction time is preferably 1 to 8 hours.
  • the catalyst used and/or acid produced are washed with water or otherwise removed, and the solvent and excessive naphthol are removed under reduced pressure to give the intended resin of formula (II).
  • resin represented by formula (II) includes the resins represented by formulae (V) and (VI): wherein n represents a mean value and ranges from 0 to 10.
  • resin of formula (II) can be reacted with an epihalohydrin compound in the presence of a basic compound to readily give the epoxy resin represented by formula (III).
  • the epihalohydrin compound include epichlorohydrin, epibromohydrin, epiiodohydrin or mixtures thereof, among which epichlorohydrin is industrially preferable.
  • the resin of formula (II) is reacted with an epihalohydrin compound in molar excess of the hydroxyl equivalent of the resin in the presence of a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, triethylammonium chloride; or an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, etc.
  • a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, triethylammonium chloride
  • an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide, etc.
  • reaction When a quaternary ammonium salt is used, the reaction often stops at the stage of ring-opening addition reaction. Then, one of the above alkali metal hydroxides is added to cause a ring-closing reaction.
  • the ring-opening addition reaction and ring-closing reaction may occur at the same time.
  • the proportion of the epihalohydrin compound used is usually 1 to 50 moles, preferably 3 to 15 moles per 1 hydroxyl equivalent of the compound represented by formula (II).
  • the reaction may be promoted by alcohols such as methanol; acetone; or aprotic polar solvents such as dimethyl sulfoxide, dimethyl sulfon, dimethylformaldehyde, preferably dimethyl sulfoxide.
  • the amount of the alkali metal hydroxide used is usually 0.8 to 1.5 moles, preferably 0.9 to 1.3 moles per 1 hydroxyl equivalent of the resin of formula (II).
  • the amount thereof is usually 0.001 to 1.0 moles, preferably 0.005 to 0.5 moles per 1 hydroxyl equivalent of the resin represented by formula (II).
  • the reaction temperature is usually 30 to 130°C, preferably 40 to 120°C.
  • the reaction time is usually 1 to 10 hours, preferably 2 to 8 hours.
  • the reaction may be proceeded while removing the water produced by the reaction from the reaction system. After completion of the reaction, by-produced salt is washed with water, filtered or otherwise removed, to give the epoxy resin represented by formula (III).
  • the epoxy resin represented by formula (III) according to this invention may be used as component (A) alone or in combination with other epoxy resins.
  • the proportion of the epoxy resin represented by formula (III) according to this invention in the total amount of epoxy resins is preferably 30% by weight or more, especially 50% by weight or more.
  • Epoxy resins which can be used in combination with the epoxy resin represented by formula (III) according to this invention include bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, alicyclic epoxy resins, biphenyl epoxy resins, novolak-type epoxy resins, among which novolak-type epoxy resins are especially advantageous in respect of heat resistance.
  • the novolak-type epoxy resins include, for example, cresol novolak-type epoxy resins, phenol novolak-type epoxy resins, brominated phenol novolak-type epoxy resins.
  • Epoxy resins which can be used in combination are not limited to those listed above, and only one or more than one of them may be chosen.
  • the resin represented by formula (II) according to this invention serves as a hardener, and may be used as component (B) alone or in combination with other hardeners.
  • the proportion of the resin represented by formula (II) according to this invention in the total amount of hardeners is preferably 30% by weight or more, especially 50% by weight or more.
  • Hardeners which can be used in combination with the resin represented by formula (II) according to this invention include polyamine-based hardeners such as aliphatic polyamines, aromatic polyamines, polyamide polyamines; acid anhydride-based hardeners such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride; phenol-based hardeners such as phenol novolak, cresol novolak; Lewis acids such as boron trifluoride, or their salts; dicyandiamides, etc., but are not limited to these examples. And only one or more than one of them may be chosen.
  • polyamine-based hardeners such as aliphatic polyamines, aromatic polyamines, polyamide polyamines
  • acid anhydride-based hardeners such as hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride
  • phenol-based hardeners such as phenol novolak, cresol novolak
  • Lewis acids such as boro
  • the epoxy resin as component (A) includes those listed above, in addition to the epoxy resin represented by formula (III) according to this invention.
  • the hardener as component (B) includes those listed above, in addition to the resin of formula (II) according to this invention.
  • the amount of the hardener as component (B) used is preferably 0.5 to 1.5 equivalents, especially 0.6 to 1.2 equivalents per 1 epoxy equivalent of the epoxy resin of component (A).
  • cure accelerators may be used, including as non-limitative examples, imidazole compounds such as 2-methylimidazole, 2-ethylimidazole; tertiary amine compounds such as 2-(dimethylaminomethyl)phenol; triphenylphosphine compounds, etc.
  • the amount of the cure accelerator used is preferably 0.01 to 15 parts by weight, especially 0.1 to 10 parts by weight based on 100 parts by weight of the epoxy resin of component (A).
  • the epoxy resin compositions according to this invention further contain known additives including inorganic fillers such as silica, alumina, talc, glass fibers; surface-treating agents for fillers such as silane coupling agent; release agents; pigments; etc.
  • inorganic fillers such as silica, alumina, talc, glass fibers
  • surface-treating agents for fillers such as silane coupling agent
  • release agents such as pigments; etc.
  • the epoxy resin compositions according to this invention are obtained by homogeneously mixing individual components.
  • the epoxy resin compositions according to this invention are usually precured at temperatures between 130 and 170°C for 30 to 300 seconds and then postcured at temperatures between 150 and 200°C for 2 to 10 hours, to proceed a curing reaction enough to afford the cured products according to this invention.
  • the resins according to this invention can be used as epoxy resins or hardeners in a wide field requiring heat resistance, low water absorption and high adhesion. Specifically, they are useful as constituents in any kind of electric and electronic materials such as insulating materials, laminated sheets, sealing materials, etc. They can also be used in the field of molding materials, composite materials, etc.
  • Example 2 The same procedure as described in Example 1 was conducted except that the amount of 1-naphthol was changed to 432g (3.0mol), to give 450g of a product (A-2) of formula (II) according to this invention wherein all of X represent a hydrogen atom.
  • the softening point of the product (A-2) was 113°C and the hydroxyl equivalent (g/eq) was 255.
  • the value of n in formula (II) was 0.8 by GPC analysis.
  • the softening point of the product (B-2) which was an epoxy resin of formula (III) according to this invention wherein all of Y represent a hydrogen atom and n 0.8 was 91.2°C, and the epoxy equivalent (g/eq) was 336.
  • Example 5 The same procedure as described in Example 5 was conducted except that the product (A-1) was replaced by 235g of the product (A-2) obtained by Example 2 to give 277g of a product (B-4).
  • the softening point of the product (B-4) which was an epoxy resin represented by formula (III) according to this invention wherein all of Y represent a hydrogen atom and n 0.8 was 88°C, and the epoxy equivalent (g/eq) was 325.
  • the product (A-1) or (A-2) obtained by Example 1 or 2 as a hardener; cresol novolak-type epoxy resin EOCN-1020 as an epoxy resin; and 2-methylimidazole as a cure accelerator were mixed in the proportions shown as parts by weight in Table 1 and roll-milled at 70 to 80°C for 15 minutes. After cooled, the mixture was ground, tabletted, molded by a transfer molding machine, then precured at 160°C for 2 hours and postcured at 180°C for 8 hours to give a cured product (test piece) according to this invention. The water absorption and adhesion of this cured product were determined. The results are shown in Table 1.
  • the bond strength was estimated by tensile shear according to ASTM D1002.
  • the adhesion was evaluated as follows: Measured value (kg/cm 2 ) Evaluation ⁇ 40 ⁇ 40 to 80 ⁇ 80 ⁇ O.
  • Phenol novolak resin (PN(H-1)) as a hardener; the product (B-1) or (B-2) obtained by Example 3 or 4 as an epoxy resin; and 2-methylimidazole as a cure accelerator were mixed in the proportions shown as parts by weight in Table 2 and tested for the properties of the cured product according to this invention in the same way as in Examples 7 and 8. The results are shown in Table 2.
  • PN(H-1) Phenol novolac resin (manufactured by Nippon Kayaku); Hydroxyl group equivalent (g/eq) 106; Softening point 85°C.
  • EOCN1020 Cresol novolak-type epoxy resin (manufactured by Nippon Kayaku); Epoxy equivalent (g/eq) 200; Softening point 65°C.
  • EPOMIC R-301 Bisphenol A-type epoxy resin (manufactured by Mitsui Petrochemical Epoxy, Co. Ltd.); Epoxy equivalent (g/eq) 470; Softening point 68°C.
  • EPPN502 Polyepoxy compound (manufactured by Nippon Kayaku); Epoxy equivalent (g/eq) 168; Softening point 70°C. Table 1
  • the resins of formulae (II) and (III) according to this invention have high refractive indices, and the cured products thereof show a water absorption remarkably lower than conventional resins and better adhesion without deteriorating glass transition temperture and heat deformation temperature which are indicative of heat resistance.
  • the resins of this invention satisfactorily meet the recent requirements for high heat resistance, low water absorption and high adhesion, and thanks to these performances, they are very useful in a wide field, particularly as sealing materials for electric and electronic components, molding materials, optical materials or laminating materials.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)
  • Structures Or Materials For Encapsulating Or Coating Semiconductor Devices Or Solid State Devices (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
EP94910046A 1993-03-22 1994-03-18 Naphthalene-ring resin, resin composition, and cured product thereof Expired - Lifetime EP0644216B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP90955/93 1993-03-22
JP05090955A JP3132610B2 (ja) 1993-03-22 1993-03-22 ナフタレン環含有樹脂、樹脂組成物及びその硬化物
PCT/JP1994/000445 WO1994021707A1 (en) 1993-03-22 1994-03-18 Naphthalene-ring resin, resin composition, and cured product thereof

Publications (3)

Publication Number Publication Date
EP0644216A1 EP0644216A1 (en) 1995-03-22
EP0644216A4 EP0644216A4 (enrdf_load_stackoverflow) 1995-04-26
EP0644216B1 true EP0644216B1 (en) 1996-07-17

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EP94910046A Expired - Lifetime EP0644216B1 (en) 1993-03-22 1994-03-18 Naphthalene-ring resin, resin composition, and cured product thereof

Country Status (7)

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EP (1) EP0644216B1 (enrdf_load_stackoverflow)
JP (1) JP3132610B2 (enrdf_load_stackoverflow)
KR (1) KR100271774B1 (enrdf_load_stackoverflow)
CN (1) CN1041526C (enrdf_load_stackoverflow)
DE (1) DE69400309T2 (enrdf_load_stackoverflow)
TW (1) TW295592B (enrdf_load_stackoverflow)
WO (1) WO1994021707A1 (enrdf_load_stackoverflow)

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JP3476584B2 (ja) * 1995-03-03 2003-12-10 日本化薬株式会社 エポキシ樹脂、エポキシ樹脂組成物およびその硬化物
JP3575776B2 (ja) * 1995-12-28 2004-10-13 日本化薬株式会社 エポキシ樹脂、エポキシ樹脂組成物及びその硬化物
KR100975846B1 (ko) * 2006-02-28 2010-08-16 디아이씨 가부시끼가이샤 페놀 수지의 제조 방법, 및 에폭시 수지의 제조 방법
TW200842135A (en) * 2007-04-23 2008-11-01 Chang Chun Plastics Co Ltd Flame retardant resin composition
JP5433294B2 (ja) * 2009-04-30 2014-03-05 エア・ウォーター株式会社 ジヒドロキシナフタレン系重合体、その製造方法およびその用途
CN101824136B (zh) * 2010-04-02 2011-12-07 南京航空航天大学 含萘环和联苯结构环氧树脂及其合成方法
JP6403554B2 (ja) * 2013-12-04 2018-10-10 日本化薬株式会社 フェノール樹脂、エポキシ樹脂、エポキシ樹脂組成物、およびその硬化物
TWI728084B (zh) * 2016-03-30 2021-05-21 日商日鐵化學材料股份有限公司 多價羥基樹脂、其之製造方法、環氧樹脂、環氧樹脂組成物及其之硬化物
WO2020003824A1 (ja) * 2018-06-27 2020-01-02 Dic株式会社 エポキシ樹脂組成物及びその硬化物

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US3437695A (en) * 1964-10-05 1969-04-08 Phillips Petroleum Co Polymerization
JPS61138622A (ja) * 1984-12-12 1986-06-26 Agency Of Ind Science & Technol 繊維強化複合材料及びそれから得られる硬化成形物
JPS62521A (ja) * 1985-02-18 1987-01-06 Sugiro Otani 縮合多環多核芳香族樹脂の製造方法及びその製造に用いる熱硬化性組成物

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DE69400309T2 (de) 1996-11-21
CN1106194A (zh) 1995-08-02
WO1994021707A1 (en) 1994-09-29
CN1041526C (zh) 1999-01-06
EP0644216A1 (en) 1995-03-22
JP3132610B2 (ja) 2001-02-05
TW295592B (enrdf_load_stackoverflow) 1997-01-11
JPH06271654A (ja) 1994-09-27
KR100271774B1 (ko) 2000-11-15
EP0644216A4 (enrdf_load_stackoverflow) 1995-04-26
KR950701656A (ko) 1995-04-28
DE69400309D1 (de) 1996-08-22

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